Electrolysis water device

Abstract

The application provides an electrolytic water device, which comprises an anode plate, a cathode plate, a membrane electrode, and a reference electrode, wherein the cathode plate is opposite to the anode plate, the membrane electrode is located between the cathode plate and the anode plate, and the reference electrode is in contact with the membrane electrode; a through hole is formed in the cathode plate, a terminal post is installed in the through hole, the terminal post extends towards the membrane electrode and is in contact with the reference electrode. The application provides an electrolytic water device, which aims to improve the convenience of assembly and adapt to a wide range of working temperature (20-120 DEG C), while ensuring long-term stable operation. The device solves the inconvenience problem of the proton exchange membrane electrolytic cell when the reference electrode is introduced for long-term operation, and the technical problem of inaccurate anode and cathode potential measurement caused by liquid junction potential, improves the accuracy and reliability of the test. In addition, the device also has the characteristics of high stability and reliability, and provides an effective solution for the related field.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of point proton exchange membrane water electrolysis, and particularly relates to a water electrolysis device. BACKGROUND

[0002] The conversion and storage of fluctuating renewable energy has become a hot spot in industry and scientific research. Proton exchange membrane water electrolysis has good dynamic response capability, high current density and adaptability of gas pressure difference of anode and cathode, and is very suitable for coupling with intermittent renewable energy (such as wind energy or solar energy) to realize large-scale long-period energy storage.

[0003] At present, optimizing the loading of noble metals in the membrane electrode of proton exchange membrane water electrolysis is one of the keys to research and development. However, since the current electrolytic cell can only form a two-electrode system, there is internal information coupling, so it is impossible to accurately measure a single cathode or anode. In order to solve this problem, the introduction of a reference electrode can accurately obtain the potential-current density relationship of a single electrode, thereby being more conducive to the optimization of the membrane electrode.

[0004] A Chinese patent (publication number CN102478536B) discloses a method of using a proton exchange membrane electrolytic cell with an external reference electrode. The method immerses the proton exchange membrane and the external reference electrode in the electrolyte solution by extending the proton exchange membrane in the proton exchange membrane electrolytic cell, so that the external reference electrode and the anode and cathode of the electrolytic cell form a three-electrode system, thereby enabling the determination of the electrode potential of the anode and cathode. However, the assembly of the device is relatively complex, and there is a liquid junction potential between the electrolyte solution and the proton exchange membrane, thereby leading to inaccurate measurement results of the potential. Edward Brightman et al. (Electrochemistry Communications 2015 52 1-4.) introduced a detection method of introducing a reference electrode in situ in an electrolytic cell. The method establishes an ion path between the reference electrode and the working electrode by introducing a salt bridge. The specific operation is to punch a hole outside the electrolytic cell, insert a Nafion tube covered with PTFE into the hole and connect it with the working electrode, and fill the tube with 0.5M H2SO4 solution to improve the proton conductivity of the Nafion tube. The reference electrode uses a Hydroflex reversible hydrogen reference electrode. Although the principle of this method is basically the same as that of the above-mentioned patent, that is, the reference electrode is introduced after the establishment of an ion path by sulfuric acid, but there are defects. Long-term high-temperature work will cause water evaporation in the salt bridge, forming a short circuit and causing ion transmission to be blocked, so it is not suitable for long-term working conditions. SUMMARY

[0005] The application provides an electrolytic water device, aiming to improve the convenience of assembly and adapt to a wide range of working temperature (20-120℃), while ensuring long-term stable operation. The device solves the problem of inconvenience of long-term operation of the proton exchange membrane electrolytic cell when introducing the reference electrode, and the technical problem of inaccurate anode and cathode potential measurement caused by liquid junction potential, improves the accuracy and reliability of measurement. In addition, the device is highly stable and reliable, providing an effective solution for the related field.

[0006] The application provides an electrolytic water device, comprising:

[0007] An anode plate;

[0008] A cathode plate opposite to the anode plate;

[0009] A membrane electrode between the cathode plate and the anode plate;

[0010] A reference electrode in contact with the membrane electrode;

[0011] Wherein, the cathode plate is provided with a through hole, and a terminal post is installed in the through hole, the terminal post extends towards the membrane electrode and is in contact with the reference electrode.

[0012] In some embodiments, the cathode plate has a first insulating area and a first conductive area, and the through hole is located in the first insulating area.

[0013] In some embodiments, the cathode plate includes a first mother plate and a first sub plate, the first mother plate corresponds to the first conductive area, and the first sub plate corresponds to the first insulating area.

[0014] In some embodiments, one side of the first mother plate facing the anode plate is provided with a first groove, and the bottom wall of the first groove is provided with a first through hole penetrating the first mother plate.

[0015] The first sub plate is installed in the first groove, and the first sub plate is provided with a second through hole penetrating the first sub plate, the second through hole and the first through hole are in communication with each other and form the through hole.

[0016] In some embodiments, the terminal post includes a first part and a second part;

[0017] The first part is located in the first through hole, and the second part is located in the second through hole;

[0018] The second through hole is provided with an internal thread, and the second part is provided with an external thread matched with the internal thread.

[0019] In some embodiments, the first conductive area is provided with a first flow channel, and the first insulating area is provided with a second flow channel surrounding the through hole.

[0020] In some embodiments, the first flow channel and the second flow channel are in communication with each other, the first flow channel has a first hydrogen gas inlet, and the second flow channel has a first flow outlet.

[0021] In some embodiments, the first flow channel and the second flow channel are separated from each other.

[0022] The cathode plate has a first inflow sub-port, a first outflow sub-port, a second inflow sub-port, and a second outflow sub-port, the first flow channel communicates the first inflow sub-port and the first outflow sub-port, and the second flow channel communicates the second inflow sub-port and the second outflow sub-port.

[0023] In some embodiments, the anode plate has a second insulating region and a second conductive region.

[0024] The second insulating region is opposite to the first insulating region, and the second conductive region is opposite to the first conductive region.

[0025] In some embodiments, the anode plate includes a second mother plate and a second sub-plate, the second mother plate corresponds to the second conductive region, and the second sub-plate corresponds to the second insulating region.

[0026] In some embodiments, the second mother plate is provided with a second groove on one side thereof facing the cathode plate, and the second sub-plate is installed in the second groove.

[0027] In some embodiments, the second conductive region is provided with a third flow channel, and the second insulating region is provided with a fourth flow channel.

[0028] In some embodiments, the third flow channel and the fourth flow channel are in communication with each other, the third flow channel has a second inlet, and the fourth flow channel has a second outlet.

[0029] In some embodiments, the third flow channel and the fourth flow channel are separated from each other.

[0030] The third flow channel has a third inflow sub-port and a third outflow sub-port.

[0031] In some embodiments, a bottom wall of the second groove is provided with a discharge port, the discharge port is opposite to the second outlet and in communication with the second outlet.

[0032] In some embodiments, the membrane electrode includes an anode catalyst layer, a cathode catalyst layer, and a proton exchange membrane between the anode catalyst layer and the cathode catalyst layer.

[0033] The anode catalyst layer is provided with an anode diffusion layer on a side thereof facing away from the proton exchange membrane, and the cathode catalyst layer is provided with a cathode diffusion layer on a side thereof facing away from the proton exchange membrane.

[0034] In some embodiments, the cathode catalyst layer includes a cathode catalyst layer and a reference electrode catalyst layer, the cathode catalyst layer is arranged on the proton exchange membrane in a spaced manner, and the reference electrode catalyst layer is opposite to the through hole.

[0035] The cathode diffusion layer comprises a first diffusion layer opposite to the cathode catalytic layer, and a reference electrode diffusion layer opposite to the reference electrode catalytic layer, and the reference electrode diffusion layer is arranged spaced apart from the cathode plate.

[0036] In some embodiments, the reference electrode is in contact with the proton exchange membrane.

[0037] In some embodiments, the reference electrode is a reversible hydrogen electrode.

[0038] In some embodiments, the active area material of the reference electrode is a platinum-coated titanium felt or a platinum-containing carbon paper, a Pt / C catalytic layer, or a series of platinum-containing substances.

[0039] In some embodiments, the terminal post comprises a post body, and an insulating layer is coated on the outer surface of the post body.

[0040] In some embodiments, a first insulating gasket and a second insulating gasket are further included.

[0041] The first insulating gasket is located between the anode plate and the membrane electrode, and the second insulating gasket is located between the cathode plate and the membrane electrode.

[0042] The prior art uses an external reference electrode to measure the potential based on the transmission of ions in the liquid electrolyte. However, under the usual electrolytic cell test conditions, the temperature is as high as 60-80℃, which will cause the electrolyte to change differently due to the influence of temperature, such as forming an ion "break" or changing the concentration, thereby causing errors in the test results. In contrast, the water electrolysis device provided in the present application only needs to continuously provide stable saturated humid hydrogen to perform potential measurement, without complex operation, and can also maintain stability for a long time.

[0043] The device is provided by opening a through hole on the cathode plate and installing a terminal post in the through hole, so that the terminal post is in contact with the reference electrode and extends to the membrane electrode. Compared with the traditional salt bridge method of introducing a reference electrode, the device can adapt to a wider range of working temperature (20-120℃), effectively avoiding the influence of liquid junction potential on the measurement results, and improving the accuracy of anode and cathode potential measurement. At the same time, by uniformly passing saturated humid hydrogen into the reference electrode area, the reference electrode has a stable environment, thereby further improving the potential stability and measurement accuracy.

[0044] The reference electrode principle mentioned in the device can be understood as a reversible reference electrode. The main components are divided into three parts: 1. PTE (porous transport electrode): Pt / C catalyst and ionomer are loaded on the porous transport layer; 2. terminal post; 3. joint layer shell. PTE provides a stable potential core component for the reference electrode. The PTE provides a stable potential by passing in saturated humid hydrogen. The PTE potential itself is determined by the pH of the ionomer contacted by the PTE, the internal environmental pressure and temperature. BRIEF DESCRIPTION OF DRAWINGS

[0045] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0046] Figure 1 is a structural schematic diagram of an electrolytic water device provided in the embodiments of the present application;

[0047] Figure 2 is a structural schematic diagram of a cathode plate provided in the embodiments of the present application;

[0048] Figure 3 is an exploded schematic diagram of a cathode plate provided in the embodiments of the present application;

[0049] Figure 4 is a structural schematic diagram of a terminal post provided in the embodiments of the present application;

[0050] Figure 5 is a structural schematic diagram of an anode plate provided in the embodiments of the present application;

[0051] Figure 6 is an exploded schematic diagram of an anode plate provided in the embodiments of the present application;

[0052] Figure 7 is another exploded schematic diagram of a cathode plate provided in the embodiments of the present application;

[0053] Figure 8 is another exploded schematic diagram of an anode plate provided in the embodiments of the present application;

[0054] Figure 9 is a schematic diagram of the anode decay rate of the electrolytic water device provided in the embodiments of the present application;

[0055] Figure 10 is a schematic diagram of the cathode decay rate of the electrolytic water device provided in the embodiments of the present application;

[0056] Figure 11 is a schematic diagram of voltage-current density relationship of the water electrolysis device provided in the embodiments of the present application;

[0057] Figure 12 is a schematic diagram of voltage-current density relationship of the anode plate provided in the embodiments of the present application;

[0058] Figure 13 is a schematic diagram of voltage-current density relationship of the cathode plate provided in the embodiments of the present application;

[0059] Figure 14 is a high-frequency resistance diagram of the No. 1 electrolytic cell provided in the embodiments of the present application;

[0060] Figure 15 is a high-frequency resistance diagram of the No. 2 electrolytic cell provided in the embodiments of the present application;

[0061] Figure 16 is a high-frequency resistance diagram of the No. 3 electrolytic cell provided in the embodiments of the present application.

[0062] wherein 10 is an anode plate, 101 is a second conductive area, 1011 is a third flow channel, 1012 is a third inflow sub-port, 1013 is a third outflow sub-port, 102 is a second insulating area, and 1021 is a fourth flow channel;

[0063] 11 is a second mother plate, 111 is a second recess, 112 is a second connecting hole, 113 is a second inflow port, 114 is a discharge port, 12 is a second sub-plate, and 121 is a second outflow port;

[0064] 20 is a cathode plate, 200 is a through hole, 201 is a first conductive area, 2011 is a first flow channel, 2012 is a first inflow sub-port, 2013 is a first outflow sub-port, 2014 is a second inflow sub-port, 2015 is a second outflow sub-port, 202 is a first insulating area, and 2021 is a second flow channel;

[0065] 21 is a first mother plate, 211 is a first recess, 212 is a first through hole, 213 is a first connecting hole, 214 is a first hydrogen gas inflow port, 22 is a first sub-plate, 221 is a second through hole, and 222 is a first outflow port;

[0066] 30 is a membrane electrode, 31 is a proton exchange membrane, 32 is an anode catalyst layer, 33 is a cathode catalyst layer, 331 is a cathode catalyst layer, 332 is a reference electrode catalyst layer, 34 is an anode diffusion layer, and 35 is a cathode diffusion layer;

[0067] 40 is a reference electrode, 50 is a terminal post, 51 is a first part, 52 is a second part, 501 is a post body, 502 is an insulating layer, 60 is a first insulating gasket, and 70 is a second insulating gasket. DETAILED DESCRIPTION

[0068] With reference to the drawings of the embodiments of the present application, the technical solutions in the embodiments of the present application will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, any other embodiments obtained by a person of ordinary skill in the art without creative effort should fall within the scope of the present application.

[0069] In the description of the present application, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined as "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise explicitly and specifically limited.

[0070] In the present application, the word "exemplary" is used to mean "serving as an example, instance, or illustration." Any implementation described as "exemplary" in the present application is not necessarily to be construed as preferred or advantageous over other implementations. The following description is presented to enable any person skilled in the art to make and use the application. In the following description, for purposes of explanation, specific details are set forth. It will be apparent to those skilled in the art that the present application can be practiced without using these specific details. In other instances, well-known structures and processes are not described in detail in order to avoid obscuring the present application. Thus, the present application is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features presented herein.

[0071] The present application provides an electrolytic water device, which will be described in detail below. First, refer to Figure 1 , Figure 1 A structure schematic diagram of an electrolytic water device in the embodiments of the present application is shown, wherein the electrolytic water device comprises:

[0072] An anode plate 10;

[0073] A cathode plate 20, the cathode plate 20 is opposite to the anode plate 10;

[0074] a membrane electrode 30 located between the cathode plate 20 and the anode plate 10;

[0075] a reference electrode 40 in contact with the membrane electrode 30;

[0076] The cathode plate 20 is provided with a through hole 200, and a terminal post 50 is installed in the through hole 200. The terminal post 50 extends towards the membrane electrode 30 and is in contact with the reference electrode 40.

[0077] Specifically, the anode plate 10 and the cathode plate 20 are used to support the membrane electrode 30 and provide flow channels for fluids (such as water, hydrogen, or oxygen) to facilitate uniform distribution and full participation in electrochemical reactions. The anode plate 10 has a water inlet and an outlet, and the cathode plate 20 has a hydrogen outlet. During the electrolysis of water, water flows between the anode plate 10 and the membrane electrode 30, and reacts to generate oxygen and protons. The protons are transported to the cathode plate 20 through the membrane electrode 30 and combine with electrons to generate hydrogen, which is finally discharged through the hydrogen outlet of the cathode plate 20, while the remaining water and oxygen are discharged through the outlet of the anode plate 10.

[0078] The electrolysis reaction occurs at the membrane electrode 30, which decomposes water into oxygen and protons at the anode active area of the membrane electrode 30, and transports the protons from the anode active area to the cathode active area of the membrane electrode 30, where hydrogen is generated. In some embodiments of the present application, the membrane electrode 30 includes an anode catalyst layer 32, a cathode catalyst layer 33, and a proton exchange membrane 31 located between the anode catalyst layer 32 and the cathode catalyst layer 33. The anode catalyst layer 32 is provided with an anode diffusion layer 34 on the side away from the proton exchange membrane 31, and the cathode catalyst layer 33 is provided with a cathode diffusion layer 35 on the side away from the proton exchange membrane 31. During the electrolysis of water, the anode diffusion layer 34 disperses water and fully contacts the anode catalyst layer 32 to generate oxygen and protons, which are transported through the proton exchange membrane 31 to the cathode catalyst layer 33, where they react with electrons to generate hydrogen, which is transported through the cathode diffusion layer 35 to the flow channel of the cathode plate 20 and finally converges and is discharged.

[0079] In some embodiments of the present application, the anode diffusion layer 34 can be a series of titanium-based porous diffusion layers such as titanium mesh and titanium felt. The cathode diffusion layer 35 can be a porous diffusion layer such as carbon paper, carbon felt, microporous diffusion layer carbon paper, titanium mesh, titanium felt, and stainless steel felt. In some embodiments of the present application, for example, for embodiments in which the anode diffusion layer 34 is titanium felt, the surface of the titanium felt is plated with a layer of corrosion-resistant noble metal such as platinum or gold to prevent passivation corrosion of the anode diffusion layer 34 under high anode potential for a long time.

[0080] The reference electrode 40 is a reference electrode for measuring the electrode potential of the water electrolysis device. Since the potential of the reference electrode 40 is known, the electromotive force values of the cathode and the anode in the electrolytic cell can be determined. In some embodiments of the present application, for example, for embodiments in which the membrane electrode 30 includes a proton exchange membrane 31, the reference electrode 40 can be in contact with one side of the proton exchange membrane 31 facing the cathode plate 20. In some embodiments of the present application, for example, for embodiments in which the membrane electrode 30 includes a reference electrode catalyst layer 332, the reference electrode 40 can be in contact with one side of the reference electrode catalyst layer 332 facing the cathode plate 20. In some embodiments of the present application, the reference electrode 40 can be in contact with one side of the cathode diffusion layer 35 facing the cathode plate 20.

[0081] In embodiments of the present application, by opening a through hole 200 on the cathode plate 20 and installing a terminal post 50 in the through hole 200, the terminal post 50 extends towards the membrane electrode 30 and is in contact with the reference electrode 40. Since the reference electrode 40 is in contact with one side of the membrane electrode 30 facing the cathode plate 20, saturated humid hydrogen gas is introduced into the reference electrode chamber formed by the reference electrode 40 and the cathode plate 20. The reference electrode 40 is surrounded by hydrogen gas to provide a stable potential and is in direct contact with the membrane electrode 30, avoiding the influence of the liquid junction potential introduced by the external reference electrode on the reference electrode, which ultimately leads to inaccurate measurement of the anode potential and the cathode potential.

[0082] At the same time, the prior art uses an external reference electrode to measure the potential based on the transport of ions in the liquid electrolyte. However, under the usual test conditions of the electrolytic cell, the temperature is as high as 60-80℃, which can cause different changes in the electrolyte affected by the temperature, such as the formation of ion "break" or changes in concentration, which in turn leads to errors in test results. In contrast, the water electrolysis device provided by the present application can adapt to a wider range of operating temperature (20℃-120℃), and only needs to continuously provide stable saturated humid hydrogen gas for potential measurement, without the need for complex operations, and can also be stable for a long time.

[0083] In some embodiments of the present application, reference is made to Figure 2 , Figure 2 A schematic diagram of a structure of the cathode plate 20 in embodiments of the present application is shown, in which the cathode plate 20 has a first conductive region 201 and a first insulating region 202, and the through hole 200 is located in the first insulating region 202. The first insulating region 202 of the cathode plate 20 has good insulating properties, while the first conductive region 201 has good conductive properties. When the terminal post 50 is installed in the through hole 200 of the first insulating region 202, the potential of the cathode plate 20 itself can be avoided to affect the potential of the terminal post 50, thereby causing the potential of the reference electrode 40 in contact with the terminal post 50 to be unstable and leading to inaccurate measurement of the anode potential and the cathode potential.

[0084] In some embodiments of the present application, the reference electrode 40 is opposite to the first insulating region 202, and the shape and size of the reference electrode 40 can be consistent with the shape and size of the first insulating region 202.

[0085] In some embodiments of the present application, referring to Figure 2 , the first insulating region 202 is located in the first conductive region 201. It can be understood that the first insulating region 202 and the first conductive region 201 can also be arranged adjacent or spaced.

[0086] Further, as an exemplary embodiment of the cathode plate 20 having the first conductive region 201 and the first insulating region 202, referring to Figure 3 , Figure 3 An exploded schematic view of the cathode plate 20 in the embodiments of the present application is shown, wherein the cathode plate 20 includes a first mother plate 21 corresponding to the first conductive region 201 and a first daughter plate 22 corresponding to the first insulating region 202. The first mother plate 21 is made of conductive carbonaceous material or metal material, such as graphite, molded carbon, aluminum, nickel, titanium or stainless steel, and the first daughter plate 22 is made of insulating material, such as polytetrafluoroethylene material or rubber, etc. By combining the first mother plate 21 and the first daughter plate 22 to form a combined cathode plate 20, the cathode plate 20 can have the first conductive region 201 and the first insulating region 202, which makes the assembly of the electrolytic water device more convenient compared with the conventional introduction of the reference electrode.

[0087] It can be understood that the cathode plate 20 can also be directly integrated into the first conductive region 201 and the first insulating region 202, such as by 3D printing to prepare an integrated cathode plate 20.

[0088] Further, in some embodiments of the present application, for example, for the embodiment in which the first insulating region 202 is located in the first conductive region 201, referring to Figure 3The first female plate 21 is provided with a first recess 211 on the side of the first female plate 21 facing the anode plate 10, and the bottom wall of the first recess 211 is provided with a first through hole 212 penetrating the first female plate 21. The first sub-plate 22 is installed in the first recess 211, and the first sub-plate 22 is provided with a second through hole 221 penetrating the first sub-plate 22, and the second through hole 221 and the first through hole 212 are in communication with each other and form a through hole 200. By embedding the first sub-plate 22 in the first recess 211 of the first female plate 21, the side of the first sub-plate 22 and the first female plate 21 facing the anode plate 10 can be flat, and the assembly difficulty of the electrolytic water device can be reduced. At the same time, since the first sub-plate 22 is embedded in the first recess 211 of the first female plate 21, the first sub-plate 22 and the first female plate 21 have a nearly horizontal contact surface and a nearly vertical contact surface, which can enhance the sealing performance of the first sub-plate 22 and the first female plate 21, and avoid the phenomenon of hydrogen leakage of the combined cathode plate 20. In addition, since the second through hole 221 and the first through hole 212 are in communication with each other and form a through hole 200, the installation of the terminal post 50 will not be affected.

[0089] It can be understood that in some embodiments of the present application, for example, for embodiments in which the first insulating region 202 and the first conductive region 201 can also be arranged adjacent to each other, the first female plate 21 can also be spliced adjacent to the first sub-plate 22 to form the cathode plate 20; or the first sub-plate 22 and the first female plate 21 can also form a stepped sealing surface or install a sealing ring to further improve the sealing performance between the first female plate 21 and the first sub-plate 22.

[0090] Further, continuing to refer to Figure 3 and Figure 4 , Figure 4 shows a structure schematic diagram of the terminal post 50 in the embodiments of the present application, wherein the terminal post 50 includes a first part 51 and a second part 52. The first part 51 is located in the first through hole 212 and is annularly spaced, and the second part 52 is located in the second through hole 221. The second through hole 221 is provided with an internal thread, and the second part 52 is provided with an external thread matched with the internal thread. Since the second part 52 of the terminal post 50 is threadedly matched with the second through hole 221 of the first sub-plate 22, on the one hand, it can facilitate the installation of the terminal post 50, and on the other hand, the multiple contact surfaces of the thread can also enhance the sealing performance of the terminal post 50 at the first sub-plate 22. In addition, since the column body 501 of the terminal post 50 is located inside the insulating layer 502, the phenomenon of electrical contact between the first female plate 21 and the terminal post 50 can be avoided.

[0091] It can be understood that the terminal post 50 can also be installed in the first through hole 212 and the second through hole 221 through other movable assembly modes, for example, a key groove is provided on the terminal post 50, and the terminal post 50 is installed in the first through hole 212 and the second through hole 221 through key groove connection.

[0092] In some embodiments of the present application, for example, for the embodiment that the cathode plate 20 has the first conductive region 201 and the first insulating region 202, referring to Figure 2 , the first flow channel 2011 is arranged in the first conductive region 201, and the second flow channel 2021 surrounding the through hole 200 is arranged in the first insulating region 202, and the second flow channel 2021 and the first flow channel 2011 are in communication with each other. In the process of electrolyzing water, the first flow channel 2011 in the first conductive region 201 delivers hydrogen to the second flow channel 2021, and since the second flow channel 2021 is arranged around the through hole 200, the contact area between the reference electrode 40 and hydrogen can be increased, so that the reference electrode 40 itself is more easily saturated with hydrogen, thereby ensuring the stability of the potential of the reference electrode 40 itself.

[0093] It can be understood that the flow channel shape of the first conductive region 201 can also be other shapes, such as a plurality of straight flow channels arranged side by side, a dot matrix-shaped flow channel, and a serpentine-shaped flow channel, etc.

[0094] In some embodiments of the present application, referring to Figure 3 , the first flow channel 2011 has a first hydrogen flow inlet 214, and the second flow channel 2021 has a first flow outlet 222, and the first hydrogen flow inlet 214 serves as the inlet of the overall flow channel of the first flow channel 2011 and the second flow channel 2021, so that the fluid flows from the first hydrogen flow inlet 214, then through the first flow channel 2011 and the second flow channel 2021 in turn, and flows to the first flow outlet 222 and is discharged.

[0095] It can be understood that the positions of the first hydrogen flow inlet 214 and the first flow outlet 222 can be changed, for example, the first hydrogen flow inlet 214 is arranged in the region of the first conductive region 201 other than the first flow channel 2011; and for example, the first flow outlet 222 is arranged in the region of the first insulating region 202 other than the second flow channel 2021.

[0096] In some embodiments of the present application, for example, for the embodiment that the first flow channel 2011 is arranged in the first conductive region 201, and the second flow channel 2021 surrounding the through hole 200 is arranged in the first insulating region 202, referring to Figure 7 , Figure 7Another exploded schematic view of the cathode plate 20 in some embodiments of the present application is shown, in which the first flow channel 2011 is separated from the second flow channel 2021. The cathode plate 20 has a first inflow sub-port 2012, a first outflow sub-port 2013, a second inflow sub-port 2014, and a second outflow sub-port 2015. The first flow channel 2011 connects the first inflow sub-port 2012 and the first outflow sub-port 2013, and the second flow channel 2021 connects the second inflow sub-port 2014 and the second outflow sub-port 2015. During electrolysis of water to produce hydrogen, the hydrogen in the first flow channel 2011 can be discharged through the first outflow sub-port 2013, and the hydrogen in the second flow channel 2021 can be discharged through the second outflow sub-port 2015. The first flow channel 2011 is separated from the second flow channel 2021, so that the potential change caused by the change in the flow rate of hydrogen in the second flow channel 2021 under different currents is avoided. By introducing saturated humid hydrogen with a stable flow rate into the second flow channel 2021, the reference electrode 40 can be better saturated with hydrogen, which is conducive to improving the stability of the reference electrode.

[0097] In some embodiments of the present application, for example, for embodiments in which the cathode plate 20 has the first conductive region 201 and the first insulating region 202, the reference electrode 40 is arranged on the first insulating region 202. Figure 5 Figure 5 A schematic view of a structure of the anode plate 10 in some embodiments of the present application is shown, in which the anode plate 10 has a second conductive region 101 and a second insulating region 102. The second insulating region 102 is opposite to the first insulating region 202, and the second conductive region 101 is opposite to the first conductive region 201. During electrolysis of water, a current is introduced between the second conductive region 101 of the anode plate 10 and the first conductive region 201 of the cathode plate 20, while almost no current is introduced between the second insulating region 102 and the first insulating region 202 due to the insulating effect, so that the influence of the current on the potential of the reference electrode 40 is avoided, thereby maintaining the stability of the potential of the reference electrode 40.

[0098] Further, in some embodiments of the present application, the reference electrode 40 is arranged on the first insulating region 202 of the cathode plate 20. Figure 6 Figure 6 ​​An exploded schematic view of the anode plate 10 in the embodiments of the present application is shown, wherein the anode plate 10 comprises a second mother plate 11 corresponding to the second conductive region 101 and a second sub-plate 12 corresponding to the second insulating region 102. The second mother plate 11 is made of a conductive carbonaceous material or a metal material, such as graphite, molded carbon, aluminum, nickel, titanium, or stainless steel, and the second sub-plate 12 is made of an insulating material, such as polytetrafluoroethylene. By combining the second mother plate 11 and the second sub-plate 12 to form the combined anode plate 10, the anode plate 10 has the second conductive region 101 and the second insulating region 102, which makes the assembly of the water electrolysis device simpler than the conventional introduction of a reference electrode.

[0099] It can be understood that the anode plate 10 can also be directly integrally formed with the second conductive region 101 and the second insulating region 102, for example, by 3D printing to prepare an integrated anode plate 10, or the second conductive region 101 and the second insulating region 102 of the anode plate 10 can also be arranged adjacent to or spaced apart.

[0100] Further, in some embodiments of the present application, referring to Figure 6 , the second mother plate 11 has a second groove 111 on the side facing the cathode plate 20, and the second sub-plate 12 is installed in the second groove 111. By embedding the second sub-plate 12 in the second groove 111 of the second mother plate 11, the side of the second sub-plate 12 and the second mother plate 11 facing the anode plate 10 is substantially flat, thereby forming flow channels that are in communication with each other on the second sub-plate 12 and the second mother plate 11, which makes the assembly of the water electrolysis device simpler than the conventional introduction of a reference electrode.

[0101] It can be understood that, in some embodiments of the present application, for example, for embodiments in which the second conductive region 101 and the second insulating region 102 can also be arranged adjacent to each other, the second mother plate 11 and the second sub-plate 12 can also be spliced adjacent to each other to form the anode plate 10.

[0102] In some embodiments of the present application, referring to Figure 5 and Figure 6 , the second conductive region 101 is provided with a third flow channel 1011, and the second insulating region 102 is provided with a fourth flow channel 1021, and the third flow channel 1011 and the fourth flow channel 1021 are in communication with each other. In the process of electrolyzing water, the fluid flows from the fourth flow channel 1021 into the third flow channel 1011, so as to facilitate the rapid diffusion of the fluid into the region of the membrane electrode 30 opposite to the anode plate 10.

[0103] It can be understood that the first flow channel 2011, the third flow channel 1011 and the fourth flow channel 1021 are serpentine flow channels, and the second flow channel 2021 is a ring-shaped flow channel. In fact, the flow channel shape can also be other shapes, such as a plurality of linear flow channels arranged side by side, a ring-shaped flow channel, or a serpentine flow channel, etc.

[0104] In some embodiments of the present application, referring to Figure 6 , the third flow channel 1011 has a second flow inlet 113, and the fourth flow channel 1021 has a second flow outlet 121. The second flow inlet 113 serves as an inlet of the third flow channel 1011 and the fourth flow channel 1021 as a whole, so that the fluid flows from the second flow inlet 113, then sequentially through the third flow channel 1011 and the fourth flow channel 1021 to the second flow outlet 121 and is discharged.

[0105] It can be understood that the positions of the second flow inlet 113 and the second flow outlet 121 can be changed. For example, the second flow inlet 113 is arranged in the second conductive area 101 except the third flow channel 1011. For another example, the second flow outlet 121 is arranged in the second insulating area 102 except the fourth flow channel 1021.

[0106] In some embodiments of the present application, continuing to refer to Figure 6 , the bottom wall of the second groove 111 is provided with a discharge outlet 114, which is opposite to the second flow outlet 121 and communicates with each other. In the process of electrolyzing water, the fluid flows from the second flow inlet 113 into the third flow channel 1011 of the anode plate 10, then flows into the fourth flow channel 1021, and finally sequentially passes through the second flow outlet 121 and the discharge outlet 114 to be discharged, so as to realize the circulation of the fluid on the anode plate 10.

[0107] Further, in some embodiments of the present application, for example, for the embodiment in which the third flow channel 1011 is arranged in the second conductive area 101, and the fourth flow channel 1021 is arranged in the second insulating area 102, referring to Figure 8 , Figure 8 Another structure of the anode plate 10 in the embodiments of the present application is shown, in which the third flow channel 1011 and the fourth flow channel 1021 are separated from each other, and the third flow channel 1011 has a third flow inlet sub-port 1012 and a third flow outlet sub-port 1013. In the process of electrolyzing water to produce hydrogen, the third flow channel 1011 flows into the electrolyzed water through the third flow inlet sub-port 1012, and circulates through the third flow outlet sub-port 1013. The water in the third flow channel 1011 wets the membrane electrode 30 and serves as a reactant.

[0108] In some embodiments of the present application, referring to Figure 1The cathode catalyst layer 33 is arranged on the proton exchange membrane 31, and includes a cathode catalyst layer 331 opposite the through hole 200, and a reference electrode catalyst layer 332 opposite the cathode plate 20. The cathode diffusion layer 35 includes a first diffusion layer opposite the cathode catalyst layer 331, and a reference electrode diffusion layer opposite the reference electrode catalyst layer 332, and the reference electrode diffusion layer is spaced apart from the cathode plate 20. Since the cathode catalyst layer 331 and the reference electrode catalyst layer 332 are spaced apart, and the first diffusion layer and the reference electrode diffusion layer are spaced apart, the cathode catalyst layer 331 and the reference electrode catalyst layer 332 are electrically insulated, and the first diffusion layer and the reference electrode diffusion layer are electrically insulated. Since the reference electrode catalyst layer 332 is opposite the through hole 200, and the reference electrode diffusion layer is spaced apart from the cathode plate 20, the reference electrode catalyst layer 332 is electrically insulated from the cathode plate 20, and direct electrical contact between the reference electrode 40 and the cathode plate 20 can be avoided to prevent the potential measurement from being deviated.

[0109] In some embodiments of the present application, for example, for embodiments in which the cathode plate 20 has the first conductive area 201 and the first insulating area 202, the shape and size of the reference electrode catalyst layer 332 and the reference electrode diffusion layer are the same as or smaller than the first insulating area 202. In some embodiments of the present application, for example, for embodiments in which the cathode plate 20 includes the first mother plate 21 and the first sub-plate 22, the shape and size of the reference electrode catalyst layer 332 and the reference electrode diffusion layer are the same as or smaller than the first sub-plate 22.

[0110] In some embodiments of the present application, the reference electrode 40 is a reversible hydrogen electrode, and preferably, the material of the reference electrode 40 is a platinum mesh, a platinum-coated titanium felt, a platinum-sprayed carbon paper, a Pt / C catalyst layer, or other platinum-containing substances.

[0111] In some embodiments of the present application, referring to Figure 4 The terminal post 50 includes a post body 501, and an insulating layer 502 is coated on the outer surface of the post body 501. The post body 501 can be a carbon rod or a copper post, and the insulating layer 502 can be made of polytetrafluoroethylene or polyether ether ketone, or other insulating substances. The insulating layer 502 can protect the post body 501 and prevent the post body 501 from being in electrical contact with the cathode plate 20 (for example, the first mother plate 21).

[0112] In some embodiments of the present application, continuing to refer to Figure 1, the electrolytic water device further comprises a first insulating gasket 60 and a second insulating gasket 70. The first insulating gasket 60 is located between the anode plate 10 and the membrane electrode 30, and the second insulating gasket 70 is located between the cathode plate 20 and the membrane electrode 30. The first insulating gasket 60 can avoid the direct electrical contact between the anode plate 10 and the membrane electrode 30, and the second insulating gasket 70 can avoid the direct electrical contact between the cathode plate 20 and the membrane electrode 30. Meanwhile, the first insulating gasket 60 and the second insulating gasket 70 can also seal the gap between the anode plate 10, the membrane electrode 30 and the cathode plate 20, thereby ensuring the stability of the entire electrolytic water device.

[0113] In some embodiments of the present application, reference is made to Figure 3 With Figure 6 , the first base plate 21 of the cathode plate 20 is further provided with a first connecting hole 213, and the second base plate 11 of the anode plate 10 is further provided with a second connecting hole 112 opposite to the first connecting hole 213. The first connecting hole 213 and the second connecting hole 112 are connected by bolts, so as to clamp the membrane electrode 30, the first insulating gasket 60 and the second insulating gasket 70 between the anode plate 10 and the cathode plate 20.

[0114] It is worth noting that the above-mentioned content about the electrolytic water device is intended to clearly illustrate the implementation and verification process of the present application. Those skilled in the art can make equivalent modifications and designs under the guidance of the present application. For example, the insulating layer 502 of the terminal post 50 is made of rubber material. For another example, the reference electrode 40 is a quasi-reference electrode (QRE) such as a carbon wire or a gold wire.

[0115] Further, in order to better implement the electrolytic water device in the present application, the present application further provides a specific implementation of an electrolytic water device test process, wherein the electrolytic water device test process comprises:

[0116] Firstly, the catalyst is loaded on the proton exchange membrane. As an exemplary embodiment, the catalyst can be made into a uniformly dispersed slurry by ball milling method, and then scraped onto a PTFE substrate. As another exemplary embodiment, the catalyst layer can be transferred to the proton exchange membrane 31 by thermal transfer printing method. In this embodiment, the anode catalyst of the membrane electrode 30 is a commercial JMIrO2 / TiO2 supported catalyst, and the noble metal content is 75wt% Ir. The cathode catalyst is a Pt / C catalyst of JM company, and the Pt content is 60wt%.

[0117] Specifically, the catalyst can be dispersed in Nafion resin and prepared into a slurry for preparing a membrane electrode (MEA), and a catalyst layer with different Nafion contents is prepared. In this embodiment, the anode catalyst content is 1±0.05mg Ir cm -2, the anode Nafion content is 10%; the catalyst content in the cathode catalytic layer is 0.5±0.05 mg Pt cm -2 , the cathode Nafion content is 24% (I:C=0.6:1).

[0118] Secondly, the three prepared identical membrane electrodes 30 are assembled with the anode plate 10 and the cathode plate 20 (MEA, Membrane Electrolyst Assembly) into electrolytic water devices, which are respectively No. 1 electrolytic tank, No. 2 electrolytic tank and No. 3 electrolytic tank. The structure of the electrolytic water device is shown in Figure 1 , which comprises a cathode plate 20, a cathode diffusion layer 35, a cathode catalyst layer 33, a proton exchange membrane 31, an anode catalyst layer 32, an anode diffusion layer 34 and an anode plate 10 in sequence.

[0119] Thirdly, deionized water (conductivity less than 1 μS / cm) at 80℃ is introduced into one side of the membrane electrode 30 on the anode plate 10 for 12 hours to make the membrane wet, and saturated and humidified hydrogen is introduced into the reference electrode 40 area at a constant speed. The proton exchange membrane 31 is completely activated by alternating operation at different current densities, and the electrochemical parameters of No. 1 electrolytic tank, No. 2 electrolytic tank and No. 3 electrolytic tank are measured by the reference electrode 40. Specifically, the current density-potential curve of the cathode and the anode at different current densities can be obtained by polarization curve test, and the resistance in the resistance correction voltage can be obtained by electrochemical impedance spectroscopy test.

[0120] Further, the three-electrode electrolytic water test device is assembled according to the above-mentioned first step, second step and third step, and the durability of the device is verified under the experimental conditions of a current density of 2 A / cm 2 , a temperature of 80℃ and a water flow rate of 50 mL / min. Referring to Figure 9 and Figure 10 , Figure 9 shows a schematic diagram of the anode decay rate of the electrolytic water device in the embodiment of the application, Figure 10 shows a schematic diagram of the cathode decay rate of the electrolytic water device in the embodiment of the application. As can be seen, the anode 1000h decay rate of the electrolytic water device is 46.01 μV / h, the anode decay rate is 40.45 μV / h, and the cathode decay rate is -5.37 μV / h. The total decay of the anode and the cathode test is 45.82 μV / h, and the error of the two-electrode test is 4.13%, so the electrolytic water device of the application can accurately distinguish the anode and cathode decay rates in the durability test process.

[0121] Continuing to refer to Figure 11 , Figure 12 and Figure 13 , Figure 11Fig. 2 shows a schematic diagram of the voltage-current density relationship of the water electrolysis device in the above embodiment, Figure 12 Fig. 3 shows a schematic diagram of the voltage-current density relationship of the anode in the above embodiment, Figure 13 Fig. 4 shows a schematic diagram of the voltage-current density relationship of the cathode in the above embodiment. Wherein, the polarization curve of the anode and the polarization curve of the cathode are substantially coincident, Figures 11-13 It can be seen that the polarization curve and the resistance corrected curve of the membrane electrode with the same catalyst loading are substantially coincident, indicating that the test has repeatability and accuracy.

[0122] Meanwhile, referring to Figure 14 , Figure 15 and Figure 16 , Figure 14 Fig. 5 shows a high-frequency resistance diagram of the No. 1 electrolytic cell in the above embodiment, Figure 15 Fig. 6 shows a high-frequency resistance diagram of the No. 2 electrolytic cell in the above embodiment, Figure 16 Fig. 7 shows a high-frequency resistance diagram of the No. 3 electrolytic cell in the above embodiment, combined with Figure 12 and Figure 13 It can be seen that the polarization curves of the anode tested by resistance correction in the three tests are substantially consistent, and the slight difference in the electrolytic cell voltage is only reflected in the cathode potential, and the high-frequency resistances of the No. 1 electrolytic cell, the No. 2 electrolytic cell and the No. 3 electrolytic cell are substantially consistent. In summary, it is proved that the water electrolysis device of the present application can well separate the anode voltage and the cathode voltage, and has good test accuracy and repeatability.

[0123] In the above embodiments, the description of each embodiment has its own emphasis, and the parts not described in detail in a certain embodiment can be seen in the detailed description of other embodiments above, which will not be repeated here.

[0124] The above has described the basic concepts, and it is obvious that the above detailed disclosure is only taken as an example and does not constitute a limitation on the present application. Although it is not explicitly stated here, those skilled in the art can make various modifications, improvements and corrections to the present application. Such modifications, improvements and corrections are suggested in the present application, so such modifications, improvements and corrections still belong to the spirit and scope of the exemplary embodiments of the present application.

[0125] Meanwhile, specific words are used in the present application to describe the embodiments of the present application. As "one embodiment", "an embodiment" and / or "some embodiments" means a certain feature, structure or characteristic related to at least one embodiment of the present application. Therefore, it should be emphasized and noted that the "an embodiment" or "one embodiment" or "one alternative embodiment" mentioned in different places in the specification does not necessarily refer to the same embodiment. In addition, some features, structures or characteristics in one or more embodiments of the present application can be properly combined.

[0126] For simplicity and to facilitate understanding of one or more embodiments of the application, the foregoing description of embodiments of the application has sometimes been presented in a manner that emphasizes certain features of the application over others. This emphasis is not intended to undermine the equal importance of other features. It will be appreciated that features of the application are susceptible to being combined in ways not specifically recited herein without departing from the spirit or scope of the application as broadly disclosed herein.

[0127] Some embodiments use numerical values to describe components, quantities of attributes. It should be understood that such numerical values used in the description of embodiments are in some examples modified by the adjectives "about", "approximately", or "substantially". Unless otherwise stated, "about", "approximately", or "substantially" indicate that the described value allows for a ±20% variation. Accordingly, numerical parameters such as those included in the application and claims are approximations that can vary depending upon the desired properties sought to be obtained by the particular embodiments. In some embodiments, numerical parameters are determined by the limitations inherent in the various components used to practice the application. Although the numerical ranges and parameters setting forth the broad scope of the application in some embodiments are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. The numerical values set forth in the specific examples are provided to be as precise as reasonably possible. However, some variations may occur depending on the choice of the desired end result.

[0128] Each patent, patent application, patent publication, and other material, such as articles, books, specifications, publications, documents, and the like, referenced herein are hereby incorporated herein by reference in their entirety for the teachings relevant to the sentence and / or paragraph in which such reference is made. Except as otherwise expressly provided herein, the contents of all such references are expressly incorporated herein by reference for all purposes. It is specifically noted that any and all articles, books, specifications, publications, documents and the like which are filed after the filing date of this application, but prior to the issuance of a patent, are specifically incorporated herein by reference in their entirety for the teachings relevant to the sentence and / or paragraph in which such reference is made. In the event that any inconsistency or conflict arises between the description, definition, and / or terminology of the application and that of the above-incorporated references, the description, definition, and / or terminology of the application shall control. In the foregoing description of an electrolytic water device according to embodiments of the present application, specific examples have been described in order to help understand the principles and embodiments of the present application. The above examples are only used to help understand the method and core idea of the present application; for those skilled in the art, the specific embodiments and application scope can be changed according to the idea of the present application. In summary, the content of the specification should not be understood as limiting the present application.

Claims

1. A water electrolysis device, characterized in that, include: Anode plate; A cathode plate, which is opposite to the anode plate; A membrane electrode, wherein the membrane electrode is located between the cathode plate and the anode plate; A reference electrode, which is in contact with the membrane electrode; The cathode plate has a through hole, and the cathode plate has a first insulating area and a first conductive area, with the through hole located within the first insulating area. A first flow channel is provided in the first conductive area, and a second flow channel is provided around the through hole in the first insulating area. The first flow channel and the second flow channel are interconnected. The first flow channel has a first hydrogen flow inlet, and the second flow channel has a first flow outlet. A terminal block is installed in the through hole within the first insulating region. The terminal block extends toward the membrane electrode and contacts the reference electrode to avoid the cathode plate's own potential affecting the terminal block's potential. During the operation of the water electrolysis device, hydrogen gas is generated at the cathode active region of the membrane electrode, and the reference electrode is surrounded by hydrogen gas to provide a stable potential for the reference electrode. The membrane electrode includes an anode catalyst layer, a cathode catalyst layer, and a proton exchange membrane located between the anode catalyst layer and the cathode catalyst layer; the anode catalyst layer has an anode diffusion layer on the side facing away from the proton exchange membrane, and the cathode catalyst layer has a cathode diffusion layer on the side facing away from the proton exchange membrane. The cathode catalyst layer includes a cathode catalyst layer and a reference electrode catalyst layer spaced apart on the proton exchange membrane, wherein the reference electrode catalyst layer is opposite to the through hole; The cathode diffusion layer includes a first diffusion layer opposite to the cathode catalyst layer and a reference electrode diffusion layer opposite to the reference electrode catalyst layer, wherein the reference electrode diffusion layer is arranged at a distance from the cathode plate.

2. The water electrolysis device as described in claim 1, characterized in that, The cathode plate includes a first mother plate and a first daughter plate, wherein the first mother plate corresponds to the first conductive area and the first daughter plate corresponds to the first insulating area.

3. The water electrolysis device as described in claim 2, characterized in that, The first mother plate has a first groove on the side facing the anode plate, and the bottom wall of the first groove has a first through hole penetrating the first mother plate; The first sub-plate is installed in the first groove. The first sub-plate is provided with a through second through hole, which is connected to the first through hole and forms the through hole.

4. The water electrolysis device as described in claim 3, characterized in that, The terminal block includes a first part and a second part; The first part is located inside the first through hole, and the second part is located inside the second through hole; The second through hole is provided with an internal thread, and the second part is provided with an external thread that mates with the internal thread.

5. The water electrolysis device as described in claim 1, characterized in that, The anode plate has a second insulating region and a second conductive region; The second insulating region is opposite to the first insulating region, and the second conductive region is opposite to the first conductive region.

6. The water electrolysis device as described in claim 5, characterized in that, The anode plate includes a second mother plate and a second daughter plate, wherein the second mother plate corresponds to the second conductive region and the second daughter plate corresponds to the second insulating region.

7. The water electrolysis device as described in claim 6, characterized in that, The second mother plate has a second groove on the side facing the cathode plate, and the second daughter plate is installed in the second groove.

8. The water electrolysis apparatus as described in claim 7, characterized in that, A third flow channel is provided in the second conductive region, and a fourth flow channel is provided in the second insulating region.

9. The water electrolysis device as described in claim 8, characterized in that, The third flow channel and the fourth flow channel are interconnected; The third flow channel has a second flow inlet, and the fourth flow channel has a second flow outlet.

10. The water electrolysis apparatus as described in claim 8, characterized in that, The third flow channel and the fourth flow channel are separated from each other; The third flow channel has a third inlet and a third outlet.

11. The water electrolysis apparatus as described in claim 9, characterized in that, The bottom wall of the second groove is provided with a discharge port, which is opposite to and connected to the second flow outlet.

12. The water electrolysis apparatus as described in claim 1, characterized in that, The reference electrode is in contact with the proton exchange membrane.

13. The water electrolysis apparatus as described in claim 1, characterized in that, The reference electrode is a reversible hydrogen electrode.

14. The water electrolysis apparatus as described in claim 13, characterized in that, The reference electrode is made of platinum-plated titanium felt, platinum-containing carbon paper, or a Pt / C catalyst layer.

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